Chen Shi-Hao, Zhang Shengye, Chen Zi-Yang, Wu Yichen, Wang Peng
State Key Laboratory of Organometallic Chemistry and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, CAS 345 Lingling Road, Shanghai 200032, P. R. China.
School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, 1 Sub-lane Xiangshan, Hangzhou 310024, P. R. China.
J Am Chem Soc. 2025 May 7;147(18):15666-15675. doi: 10.1021/jacs.5c02996. Epub 2025 Apr 28.
Here, we report the Cu-catalyzed asymmetric carbene insertion into both Ge-H and Si-H bonds with α-trifluoromethyl diazo compounds, enabled by a class of newly developed -symmetrical bisoxazoline ligands. This protocol provides an efficient method for the preparation of enantioenriched α-trifluoromethyl ogranogermanes and organosilanes, featuring a broad substrate scope, mild reaction conditions, excellent enantioselectivity, and low catalyst loading. The key to the tolerance of both Si-H and Ge-H bonds is the use of SPSiBox ligands bearing a flexible and tunable chiral pocket. Preliminary mechanistic studies and computational studies unveiled the origin of chiral induction with SPSiBox ligands, the mechanism of Cu-catalyzed Ge-H insertion. This method not only provides a new method for the construction of trifluoromethyl-containing chiral molecules but also opens a new avenue for the preparation of chiral Si- and Ge-containing functional molecules.
在此，我们报道了在一类新开发的不对称双恶唑啉配体的作用下，铜催化α-三氟甲基重氮化合物对锗氢键和硅氢键的不对称卡宾插入反应。该方法为制备对映体富集的α-三氟甲基有机锗和有机硅提供了一种有效的方法，具有底物范围广、反应条件温和、对映选择性优异和催化剂用量低的特点。硅氢键和锗氢键耐受性的关键在于使用具有灵活可调手性口袋的SPSiBox配体。初步的机理研究和计算研究揭示了SPSiBox配体的手性诱导起源以及铜催化锗氢键插入的机理。该方法不仅为构建含三氟甲基的手性分子提供了一种新方法，也为制备含手性硅和锗的功能分子开辟了一条新途径。
